Novel photographic processing compositions and improved processing using such compositions for preparing silver sound tracks

ABSTRACT

IMPROVED PHOTOGRAPHIC PROCESSING COMPOSITIONS FOR PREPARING SILVER SOUND TRACKS ARE PROVIDED WHICH CONTAIN A SILVER BLEACH INHIBITOR AND A DIFFUSIBLE ONIUM SALT. ALSO PROVIDED IS AN IMPROVED PROCESS FOR PRODUCING A SILVER SOUND TRACK IN AN EXPOSED PHOTOGRAPHIC ELEMENT HAVING AT LEAST ONE SILVER HALIDE EMULSION LAYER WHICH COMPRISES DEVELOPING THE EXPOSED ELEMENT TO FORM A PICTURE RECORD COMPRISING SILVER AND DYE AND A SOUND RECORD COMPRISING SILVER AND BLEACHING AND FIXING THE ELEMENT TO REMOVE THE SILVER OF THE PICTURE RECORD WHICH IMPROVEMENT COMPRISES SELECTIVELY CONTACTING THE SOUND TRACK RECORD PRIOR TO BLEACHING WITH A MIXTURE OF A SILVER BLEACH INHIBITOR AND A DIFFUSIBLE ONIUM SALT TO RETAIN AT LEAST A PORTION OF THE SILVER OF THE SILVER SOUND TRACK DURING THE BLEACHING.

United States Patent US. Cl. 96-4 18 Claims ABSTRACT OF THE DISCLOSUREImproved photographic processing compositions for preparing silver soundtracks are provided which contain a silver bleach inhibitor and adifiusible onium salt. Also provided is an improved process forproducing a silver sound track in an exposed photographic element havingat least one silver halide emulsion layer which comprises developing theexposed element to form a picture record comprising silver and dye and asound record comprising silver and bleaching and fixing the element toremove the silver of the picture record which improvement comprisesselectively contacting the sound track record prior to bleaching with amixture of a silver bleach inhibitor and a diffusible onium salt toretain at least a portion of the silver of the silver sound track duringthe bleaching.

This application is a continuation-in-part of my copending US. patentapplication Ser. No. 100,769 filed Dec. 22, 1970 and now abandoned.

This invention relates to photographic processes and more particularlyto an improvement in the process of developing color film with a silversound record.

A serious problem in providing color films with a silver sound trackresides in preventing loss of density of the sound track duringprocessing during the bleaching of the silver in the picture areas or offilter antihalation layers containing silver.

Previous methods of retaining the silver of the sound image haveincluded 1) redeveloping the sound image only with a viscous developerafter bleaching the film, (2) bleaching only the picture image area, (3)converting the silver of the image area to silver sulfide and (4)protecting the sound track with an adhesive tape or varnish. All ofthese approaches to the problem entail certain disadvantages such ascritical concentrations of reactants, a number of treatments to one areaonly of the film, or the use of silver sulfide which has less absorbanceof infrared radiation than silver, whereas most photocells in soundprojectors are highly sensitive to infrared radiation.

It has been found that when a developed silver image is contacted with asilver bleach inhibitor subsequent to initial devolpment and prior tobleaching, the silver is rendered unbleachable. Therefore, when only thesound track portion of a film having a silver sound record is contactedwith a silver bleach inhibitor this silver sound record is renderedunbleachable. This method is disclosed and claimed in copendingapplication Bevis, Bello and Holtz, entitled Process for Preparing ColorFilm With Silver Sound Record Using :Bleach Inhibitor, Ser. No. 100,608,filed Dec. 22, 1970, and the continuation-impart thereof filedconcurrently herewith.

It has also been found that when the sound track portion of the film iscontacted with a quaternary ammonium salt subsequent to initialdevelopment and prior to color development and/or bleaching, the silverformed in the sound image portion of the film is rendered unbleachable.

3,705,800 Patented Dec. 12, 1972 ice This method is disclosed in VogtUS. Patent 3,243,295, issued Mar. 29, 1966.

However, when the silver images are bleached with very strong highlyactive bleaching solutions, the silver sound image protected by theabove compounds is less than completely resistant to being bleached. Ittherefore appears desirable to provide an improved method for retainingthe silver of the sound image during bleaching and fixing of colorphotographic elements having such sound images.

Accordingly, it is an object of my invention to provide an improvedprocess of retaining silver sound images in color film as well as novelprocessing compositions for carrying out this process.

I have discovered that a substantial loss of density of the silver soundimage during bleaching of photographic elements having such silver soundimages can be prevented by selectively contacting the silver sound imagesubsequent to initial development and prior to bleaching with a mixtureof a silver bleach inhibitor and a diffusible onium compound. Theresults obtained by the use of the mixture of the silver bleachinhibitor and the dilfusible onium compound are well in excess of thatobtained by the use of either compound alone. In other words, theresults obtained by the use of the mixture are synergistic.

The process of the invention includes a treatment of just the soundtrack portion of the film to selectively retain the silver sound imagein the sound track portion of the film.

A wide variety of difiusible onium compounds can be utilized in thepresent invention. Such onium compounds, that is, compounds that containan organic cation, are diffusible in the hydrophilic organic colloidscomprising photographic elements in the presence of alkaline processingcompositions. Such onium compounds are typically quaternary ammoniumcompounds, quaternary phosphonium compounds or tertiary sulfoniumcompounds. The onium compounds can be used as hydroxides or as othertypes of salts such as halides. Typical suitable quaternary ammoniumcompounds have the formulas:

'\e%' N w it and III. .2:. I N w n n Typical suitable phosphoniumcompounds have the Typical suitable tertiary sulphonium compounds havethe formula:

In the above formulas:

R to R are each organic radicals such as alkyl radicals having from 1 to24 carbon atoms including substituted alkyl radicals such as aralkylradicals, or aryl radicals including substituted aryl radicals such astolyl, phenyl and the like;

W'" is an anion including hydroxyl or an anion derived from an acid suchas bromide, chloride, p-toluene sulfonate perchlorate or the like; and

Z and Z each represents the non-metallic atoms necessary to complete aheterocyclic ring generally having from 5 to and preferably from 5 to 6atoms in the heterocyclic nucleus such as carbon, nitrogen, oxygen,selenium and sulfur atoms to form such heterocyclic rings as pyridine,quinoline, benzoquinoline, oxazole, benzoxazole, selenazole,benzoselenazole, thiazole, benzothiazole, piperidine, naphthothiazole,imidazole, benzimidazole, naphthimidazole, naphthoxazole,naphthoselenazole, isoquirioline, pyrrole, pyrrolidine and the like,such heterocyclic rings being suitably substituted with suchsubstituents as halogens, lower alkyl radicals and halo-lower alkylradicals. A particularly useful class of onium compounds are thetenaalkyl quaternary ammonium compounds of Formula I wherein at leastone of the alkyl groups is a straight chain radical composed of carbonand hydrogen containing from 12 to 18 carbon atoms and wherein Xrepresents a halide.

Typical onium compounds and other materials that can be utilized in thepresent invention are listed below.

(I) Hexadecyltrimethyl ammonium bromide- (II) Trimethyllauryl ammoniumchloride (III) Trimethyl tall oil fatty ammonium chloride 1 (IV)Trioctylpropyl ammonium bromide (V) Tetrapentyl ammonium iodide (VI)(2-chloroethyl)trimethyl ammonium chloride (VII) Tetramethyl ammoniumbromide (VIII) Ethyltrimethyl ammonium iodide (1X) Trimethyl cocoammonium chloride 2 (X) Dodecyltrimethyl ammonium chloride (XI)Trimethylphenyl ammonium chloride (XII) Octadecyltrimethyl ammoniumchloride (XIII) Tetrahexyl ammonium iodide (XIV) Dodecyltrimethylammonium sulfate (XV) Dodecyltrimethyl ammonium phosphate (XVI)1-benzyl-2-picolinium bromide (XVII)1-(3-bromopropyl)-2-picolinium-p-toluenesulfonate (XVIII)l-phenethyl-Z-picolinium bromide (XIX) l-'y-phenylpropyl-2-picoliniumbromide (XX) 2,4-dimethyl-l-phenethylpyridinium bromide ()QCI)2,6-dimethyl-l-phenethylpyridinium bromide (XXII)S-ethyI-Z-methyl-l-phenethylpyridinium bromide (XXIII)a-Picoline-fl-naphthoylmethyl bromide (XXIV)1-fl-phenylcarbamoyloxyethyl-Z-picolinium bromide (XXV)Anhydro-1-(4-sulfobutyl)-2-picolinium bromide (XXVI)2-ethyl-l-phenethylpyridinium bromide (XXVII) 1-[3-(N-pyridiniumbromide) -propyl]-2- picolinium-Z-toluenesulfonate (XXVIII)1-methyl-2-pi-colinium-p-toluenesulfonate (XXIX)1-phenethyl-2,4,fi-trimethylpyridinium bromide (XXX)1-phenethyl-4-n-propylpyridinium bromide (XXXI) 4-y-hydroxypropyl-l-phenethylpyridinium bromide (XXXII)l-n-heptyl-Z-picolinium bromide (XXXIII)2-isopropyl-l-phenethylpyridinium bromide (XXXIV) Tetraphenylammoniumbromide (XXXV) Tetraethylammonium bromide (XXXVI) N-ethylpyridiniumbromide (XXXVII) N,N-diethylpiperidinium bromide (XXXVIII)Ethylene-bis-pyridinium bromide (XXXIX) 1-phenethyl-3-picolinium bromideS o51d by the General Mills Co. under the name Allquat I wherein:

(XL) Polyethylene oxide bis-pyridinium perchlorate (XLI)3-methyl-2-ethylisoquinolium bromide (XLII) 3-methylisoquinoliniummethyl-p-toluenesulfonate (XLIII)1-ethyl-2-methyl-3-phenethylbenzimidazolium bromide (XLIV)5,6-dichloro-1-ethyl-2-methyl-3-(3-sulfobutyl)- benzimidazolium betaine(XLV) Lauryldimethylsulfonium-p-toluenesulfonate (XL-VI)Nonyldimethylsulfonium-p-toluenesulfonate (XLVII)Octadimethylsulfonium-p-toluenesulfonate (XLVIII) Butyldimethylsulfoniumbromide (XLIX) Triethylsulfonium bromide (L)Dodecyldimethylsulfonium-p-toluenesulfonate (LI)Decyldimethylsulfonium-p-toluenesulfonate (LII) Phenyldimethylsulfoniumbromide (LIII) Phenethyldimethylsulfonium bromide (LIV)Tetraethylphosphonium bromide (LV)Ethylene-bis-oxymethyltriethylphosphonium bromide (LVI)Tetraphenylphosphonium bromide (LVII) Phenethyltrimethylphosphoniumbromide As used herein and in the appended claims, the term bleachinhibitor refers to an organic compound which, when dissolved in anaqueous solution at a concentration of 10- molar and mixed with an equalvolume of a 0.05% w. aqueous gelatin solution containing a concentrationof 3X10 molar silver metal particles of about 0.12 micron in diameter,which silver particles are prepared by contacting a silver nitratesolution with equal molar amounts of sodium citrate and ferrous sulfate(as described by Frens, The Reversibility of Irreversible Colloids, Ph.D. Thesis, University of Utrecht, Holland, 1968, page 27), inhibitsbleaching for a minimum of 15 minutes when there is added to the mixtureof silver particles and bleach inhibitor one volume of the followingbleach-fix bath:

1 EDTA-Ethvlenediamine tetraacetlc acid.

Bleach-fixing occurs when the mixture changes from dark brown tocolorless. A control solution which contains no bleach inhibitor becomescolorless Within four minutes.-

We have found that organic compounds which exhibit particular utility asbleach inhibitors as defined above are thioland selenol-containingcompounds such as mercaptoand selenol-substituted alkanoic acids,especially 2- mercapto-alkanoic acids, thiol-and selenol-substitutedaryls, such as thiophenols and thionaphthols, thiolandselenoI-substituted heterocyclic compounds containing 5 to 6 atoms inthe hetero ring, said ring containing at least one nitrogen atom such asmercaptobenzoxazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,mercaptothiadiazoles, mercaptotriazoles, 1-phenyl-5-mercaptotetrazolesand mercaptoquinolines, thiocarboxylic acids and esters thereof such asthiobenzoic acid and xanthates such as p0- tassium octyl xanthate.

In a preferred embodiment of our invention, the term bleach inhibitorrefers to a compound of the following general formulae:

( Ra m axn I (VII) a tA ex-xta en {-A -)XeYe a represents 0, 1,2,3, 4, 5or 6,

X represents a member selected from the group consisting of sulfur andselenium;

R R R and R each represents a member selected from the group consistingof nitro; halo (e.g., chloro, bromo, fluoro, iodo); an alkyl groupincluding substituted alkyl having from 1 to 22 carbon atoms, preferablyhaving 1 to 16 carbon atoms such as alkyl (e.g., methyl, ethyl, propyl,cyclopropyl, isopropyl, butyl, isobutyl, secbutyl, tert-butyl,cyclobutyl, pentyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, cyclohexyl,cyclohexadiene, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl and the like), haloalkyl (e.g.,fluoroalkyl, chloroalkyl, bromoalkyl, as for example, chlorooctyl,bromododecyl, fluorotetradecyl and the like), sulfoalkyl (e.g.,sulfohexyl, sulfooctyl, sulfododecyl and the like), sulfatoalkyl (e.g.,sulfatodecyl, sulfatotetradecyl and the like), alkylsulfonylalkyl (e.g.,ethylsulfonylbutyl and the like), cyanoalkyl (e.g., cyanohexyl,cyanooctyl, cyanodecyl and the like), carboxyalkyl (e.g., carboxyhexyl,carboxydecyl, carboxyhexadecyl and the like), alkoxyalkyl (e.g.,octoxyhexyl, butoxyhexyl, ethoxydecyl and the like), aryloxyalkyl (e.g.,phenoxymethyl, phenoxyethyl and the like), alkoxyaralkyl (e.g.,methoxyphenylmethyl, butoxyphenylhexyl and the like), acyloxyalkyl(e.g., benzoyloxyhexyl, acetoxybutyl and the like), alkoxycarbonylalkyl(e.g., butoxycarbonylhexyl and the like), aryloxycarbonylalkyl (e.g.,phenoxycarbonylethyl, chlorophenoxycarbonylbutyl and the like),alkylamidoalkyl (e.g., hexanamidobutyl, octanamidopropyl and the like),arylamidoalkyl (e.g., phenylamidoethyl, methylphenylamidobutyl and thelike) and the like; an aryl group including naphthyl and other fusedring aromatics and substituted aryl such as aryl (e.g., phenyl,naphthyl, anthracenyl, phenanthrenyl and the like), haloaryl (e.g.,chlorophenyl, trichlorophenyl, dibromophenyl, fluorophenyl, chlorotolyland the like), sulfoaryl (e.g., sulfophenyl and the like), sulfatoaryl(e.g., sulfatophenyl and the like), nitroaryl (e.g., nitrophenyl,dinitrophenyl and the like), cyanoaryl (e.g., cyanophenyl, cyanonaphthyland the like), carboxyaryl (e.g., carboxyphenyl, dicarboxyphenyl and thelike), alkaryl (e.g., tolyl, butylphenyl, decylphenyl, diethylphenyl,trifluoromethylphenyl and the like), aralkaryl (e.g., benzylphenyl,naphthylmethylphenyl and the like), alkoxyaryl (e.g., octoxylphenyl,methoxyphenyl and the like), aryloxyaryl (e.g., phenoxyphenyl,phenoxynaphthyl and the like), acyloxyaryl (e.g., benzoyloxyphenyl,acetyloxyphenyl and the like), alkoxycarbonylarlyl (e.g.,ethoxycarbonylphenyl and the like), aryloxycarbonylaryl (e.g.,phenoxycarbonylphenyl, methylphenoxycarbonylnaphthyl and the like),alkylamidoaryl (e.g., acetamidophenyl, amylamidophenyl,di-t-amylamidophenyl, hexanamidophenyl, heptanamidophenyl,octanamidophenyl, nonanamidophenyl, decanamidophenyl,undecanarnidophenyl, dodecanamidophenyl, tridecanamidophenyl,tetradecanamidoaryl, pentadecanamidophenyl, heptafluorobutanamidophenyl,carboxycyclopentanacetamidophenyl and the like),cycloalkyliminosulfonylaryl (e.g., piperidinylsulfonylphenyl,acetidinylsulfonylphenyl, pyrrolidinylsulfonylphenyl,indolinylsulfonylphenyl and the like) and the like; a thio groupcontaining 3 to 22 carbon atoms such as alkylthio (e.g., propylthio,hexylthio, octylthio, dodecylthio and the like), carboxyalkylthio (e.g.,carboxybutylthio, carboxyhexylthio and the like), arylthio (e.g.,phenylthio, naphthylthio, methylphenylthio and the like),alkylcarbonylalkylthio (e.g., methylcarbonylethylthio,butylcarbonylpropylthio and the like), alkylcarbonylarylthio (e.g.,methylcarbonylphenylthio, hexylcarbonyltolylthio,benzylcarbonylphenylthio and the like), arylcarbonylarylthio (e.g.,phenylcarbonylphenylthio and the like), arylcarbonylalkylthio (e.g.,phenylcarbonylmethylthio and the like) and the like; an amido groupcontaining from 4 to 22 carbon atoms such as alkylamido (e.g.,hexanamido, heptanamido, octanamido, decanamido, heptafluorobutanamidoand the like), arylamido (e.g., benzylamido and the like), alkarylamido(e.g., methylbenzylamido, butylbenzylamido,hexylbenzylamido,decylbenzylamido and the like), aralkylamido (e.g., phenacetamido,phenbutanamido, tolylhexanamido and the like), aryloxyalkylamido (e.g.,phenoxyacetamido, naphthoxyacetamido, di-t-amylphenoxyacetamido and thelike) and the like; a carbonyl group such as alkylcarbonyl (e.g.,'butylcarbonyl, heptylcarbonyl and the like), arylcarbonyl (e.g.,phenylcarbonyl, naphthylcarbonyl and the like), alkoxycarbonyl (e.g.,ethoxycarbonyl, butoXycarbonyl and the like), aryloxycarbonyl (e.g.,phenoxycarbonyl, naphthoxycarbonyl and the like) and the like; acarbamoyl group such as alkylcarbamoyl (e.g., butylcarbamoyl,hexylcarbamoyl and the like), arylcarbamoyl (e.g., phenylcarbamoyl,naphthylcarbamoyl and the like) and the like; alkoxy (e.g., ethoxy,butoxy, octoxy, benzoxy irrlid the like), and aryloxy (e.g., phenoxy,toluoxy and the R represents a member selected from the group consistingof hydrogen and an acyl group having from 1 to 22 carbon atoms includingaryloyl and alkanoyl groups (e.g., benzoyl, acetyl, propanoyl,benzothioyl, acetothioyl and the like);

Y represents a basic cation such as an alkali metal ion like sodium andpotassium, ammonium and the like;

A A A and A each represents a member selected from the group consistingof a carbonyl group C=O); a thiocarbonyl group C S); a carboxymethylenegroup CH-COOH); a carbocyclic ring containing 3 to 6 carbon atoms whichcan be part of a fused ring structure such as cycloalkylene (e.g.,cyclopropylene, cyclobutylene, cyclopentylene and cyclohexylene),cycloalkenylene (e.g., cyclopropenylene, cyclobutenylene,cyclopentenylene, cyclopentadienylene, cyclohexenylene andcyclohexadienylene) and arylene (e.g., phenylene, naphthylene,anthrylene and the like); a 3 to 6 membered heterocyclic ring containingat least one carbon atom and from 1 to 5 atoms selected from the groupconsisting of nitrogen, oxygen, sulfur and selenium which ring can haveother carbocyclic and heterocyclic rings fused to it such as oxirenyl,furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, oxazolyl,benzoxazolyl, isoxazolyl, benzisoxazolyl, oxadiazolyl, benzoxadiazolyl,1,2-pyranyl, 1,4- pyranyl, 2(H)benzopyranyl, 4(H)benzopyranyl, dioxolyl,methylenedioxybenzene, 1,2-oxazinyl, 1,3-oxazinyl, 1,4- oxazinyl,morpholinyl, 1,3-oxathianyl, 1,4-oxathianyl, 1,2- dioxanyl,1,3-dioxanyl, 1,4-dioxanyl, dioxanenyl, dioxadienyl, diazetyl, pyrrolyl,indolyl, isoindolyl, carbazolyl, pyrrocolinyl, acridinyl,phe'nanthridinyl, 2-imidazolinyl, 3- imidazolinyl, 4-imidazolinyl,pyridyl, pyridazinyl, cinnolinyl, phthalazinyl, quinoxalinyl,pyrimidinyl, pyrazolo- [3,4-d]pyrimidinyl, hypoxanthinyl,benzopyrimidinyl, pyrazinyl, quinoxalinyl, phthalazinyl, quinolinyl,isoquinolinyl, phenazinyl, phenoxazinyl, phenothiazinyl, purinyl,pteridinyl, 1,3,5-triazinyl,' 1,2,4-triazinyl, 1,2,3-triazinyl,triazolyl, benzotriazolyl, tetrazolyl, triazinthionyl, l(H)- azepinyl,piperidinyl, irnidazolidinyl, quinolizidinyl, thienyl, benzothienyl,isobenzothienyl, dibenzothienyl, thiazolyl, benzothiazolyl,isothiazolyl, benzisothiazolyl, thiadiazolyl, benzothiazolyl,1,2-dithiolyl, 1,3-dithiolyl, 1,3- oxathiolyl, thianthrinyl,thiamorpholinyl, 1,4-thianinyl, 1,4-dithanyl l,4-dithiadienyl,selenazolyl, benzoselenazolyl, isoselenazolyl, benzisoselenazolyl,selenadiazolyl, benzoselenadiazolyl and the like; such that R R R and Rdo not represent a carbonyl group, a carbamoyl group or an amido groupwhen A A A and A represent a carbonyl or thiocarbonyl and such that thegrouping R {A the grouping R {-A the grouping R l-A and the grouping R-A each represents a moiety having a molecular weight of from to 1,000and preferably from to 400 and preferably containing not more than onesolubilizing group such as carboxy unless the grouping contains ahydrophobic moiety such as a long alkyl chain or an aryl group.-

Many heterocyclic compounds having a molecular weight of less than 100(exclusive of the mercapto group) such as those compounds shown inBritish Patent 1,138,842 have been found not to be bleach inhibitors butrather bleach accelerators. Compounds of this type do not fall withinthe meaning of the term bleach inhibitor as defined herein.

In a more preferred embodiment of our invention, the bleach inhibitor isan organic compound or the salt of an organic compound as defined inFormulae VI, VII and VIII above having an acidic thiol or selenol, orhaving a group capable of forming such a compound prior to or subsequentto being brought into contact with a photographic element. For example,such thiol and selenol precursors can form the thiol or selenol groupupon hydrolysis. Examples of precursors which form acidic thiol bleachinhibitors are bleach inhibitors XCI and XCII. Another example of thiolforming compounds is disulfides (i.e., compounds of Formula VI above)which cleave at the sulfur atoms to yield at least one thiol compound.

The acidity of the thiol and selenol groups can be imparted by the groupto which these groups are attached (e.g., a heterocyclic or carbocyclicring). Alternatively, other groups attached to the group having thethiol and selenol groups can impart acidity. For example, a carboxylicacid group on a carbon atom adjacent to the atom to which these groupsare attached (e.g., Z-mercaptoluric acid) imparts the desired acidity.Other electron withdrawing groups (e.g., nitro and halo) can also impartacidity to the thiol and selenol groups.

Compounds having the following formulae exhibit particular utility asbleach inhibitors:

(A) Z-mercaptobenzoxazoles (B) Z-mercaptobenzothiazoles (C)Z-mercaptobenzimidazoles (D) Z-mercaptothiadiazoles NN HS-("J ("l-Z-Rza(E) Z-mercaptotriazoles (F) 1-phenyl-S-mercaptotetrazoles R and R eachrepresents an alkyl group having from 5 to 17 and preferably from 8 to12 carbon atoms;

Z represents sulfur or the group NHCO;

n represents 0 to 5 and preferably 1.

The following list of compounds are typical sulfur and seleniumcompounds which function as bleach inhibitors in the present invention:

(LVIII) 4-hexanamidothiobenzoic acid (LIX) 2-mercaptolauric acid (LX)n-Butylthiobenzoic acid (LXI) 4-octylthiobenzoic acid (LXII)2-naphthalenethiol (LXIII) 4-quir1olinethiol (LXIV)2,3-quinoxalinedithiol (LXV) 5-ethy1-4-'benzopyrimidinethiol (LXVI)3-mercapto-5-phenyl-1,2,4-triazole (XLVII)3-(S-mercapto-1,2,4-triazol-3-ylthio)- propanoic acid (LXVIII)1-(3,5-di-pentanamidophenyl)-5-mercaptotetrazole (LXX)1-(3-acetamidophenyl)-5-mercaptotetrazole (LXXI)1-phenyl-5-selenoltetrazole (LXXII) l-phenyl-S-mercaptotetrazole(LXXIII) 1-{3-[2-(2,4-di-t-amylphenoxy)-acetamido]-phenyl}-5-mercaptotetrazole (LXXIV) 1- [4- l-piperidinylsulfonyl-phenyl] -5- mercaptotetrazole (LXXV) 1-(l-naphthyl)-5-mercaptotetrazole (LXX'VI)1-(3-pentanamidophenyl)-5mercaptotetrazole (LXXVII)1-(3-nonanamidophenyl)-5-mercaptotetrazole (LXXVIII) 1-S-tetradecanamidophenyl -5-mercaptotetrazole (LXXIX)2-nonanamido-6-mercaptopurine (LXXX) Z-mercapto-1,3-benzoxazole (LXXXI)2-mercapto-1,3-benzothiazole (LXXXII)Z-mercapto-6-pentanamido-1,3-benzothiazole(LXXXIII)-2-mercapto-6-nonanamido-1,3-benzothiazo-le (LXXXIV)Z-mercapto-S-pentanamido-1,3,4-thiadiazole (LXXXV)Z-mercapto-S-nonanamido-1,3,4-thiadiazo1e (LXXXVI)2-mercapto-S-tetradecanamido-1,3,4-

thiadiazole (LXXXVII) Z-pentylthio-S-mercapto-1,3,4-thiadiazole(LXXXVIII) 2-octylthio-5-mercapto-1,3,4-thiadiazole (LXXXIX)2-dodecyl-5-mercapto-1,3,4-thiadiazole (XC)2,4-diamino-G-mercaptopyrimidine (XCI)2-(1-phenyltetrazol-5-ylthio)-butan-3-one (XCII) OL'(1-phenyltetrazol-5-ylthio)-ethy1-pheny1ketone (XCHI)3-decyl-2-oxirenthiol (XCIV) S-(S-trichloropentyl)-2-furanthiol (XCV)6-( IO-sulfodecyl)-2-benzofuranthiol (XCVI)6-(8-sulfatoocyl)-3-isobenzofuranthiol (XCVII)4-buty1sulfony1hexyl-l-dibenzofuranthiol (XCVIII 4- 7 -cyanoheptyl-2-oxazolthiol (XCIX) 1,3-benzoxazol-2-thiol (C)fi-pentanamido-1,3-benzoXazol-2-thiol (CI)6-nonanamido-1,3-benzoxazol-2-thiol (CII)5-pentanamido-1,3-benzoxazo1-2-thiol (CIII)8-(3-mercapto-4-isoxazolyl)-octanoic acid (CIV)7-benzyl-3-benzisoxazolthiol (CV)4-propoxypentyl-2,1,3-oXadiazol-5-thiol (CL I)17-(2-ethylenebenzoate)-2,l,3-benzoxadiazol-4- t io (CVII)4-(6-ethylhexahoate)-1,2-pyran-2-ylthiol (CVIII)4-(3-phenylpropanoate)-1,4-pyran-2-ylthiol (CIX)8-butanamidoethyl-2(H)-benzopyran-4-ylthiol (CX)4-(2-ethyl-4-sulfophenyl)-dioxazol-2-ylthiol (CXI) 5-(2,4-dinitrophenyl)-1,2-oxazin-3-ylthio1 (CXII)4-(4-butoxyphenyl)-morpholin-3-ylthiol (CXIII)4-(4-phenoxyphenyl)-1,3-diox0lan-2?ylthiol (CXIV)6-(4-phenylenebutanoate)1,3-oxathian-2- ylthiol (CXV)6-(4-phenylbenzoate)-1,2-dioxan-3-ylthiol (CXVI)4'-(S-mercapto-1,2,4-triazol-3-ylthiol)- acetophenonc (CXVII)4-(S-mercapto-l,2,4-triazol-3-ylthiol)-benzophenone (CXVII)4-decyl-l,2-diazet-3-ylthiol (CXVIII)l-(3-octanarnidophenyl)-pyrrol-2-ylthiol (CXIX)l-ethyl-3-n-octylthio-indol-2-ylthiol (CXX)2-ethyl-3butyl-isoindol-l-ylthiol (CXXI)l-methyl-4-ethyl-carbaz0l2-ylthiol (CXXII)7-butanamidopyrrocolin-3-ylthiol (CXXIII) 4-ethylacridin-2-ylthiol(CXXIV) 2-phenanthridinylthiol (CXXV)3-ethyl-4-butanamido-2-imidazolin-Z-ylthiol (CXXVI)1,3-benzimidazol-2-thiol (CXXVII) 6-acetamido-1,3-benzimidazol-2-thiol(CXXVIII) 6-nonanamido-1,3-benzimidazol-2-thiol (CXXIX)4-butyl-2rpyridinylthiol (CXXX)4-(3-hexanamidophenyl)-2-pyridazinylthiol (CXXXI)7-methylhypoxanthin-6-ylthiol (CXXXII)3-(3-hexanamidophenyl)-pyrazin-2-ylthiol(CXXXIII)-3-butyIquinoxalin-2-ylthiol (CXXXIV)1-methylphthalazin-4-ylthiol (CXXXV)S-benzylamidophenylquinolin-2-ylthiol (CXXXVI) S-butylphenazin-Z-ylthiol(CXXXVII) S-methylphenoxyazin-Z-ylthiol (CXXXVIII)-chlorophenothiazin-Z-ylthiol (CXXXIX)S-n-decylthio-1,2,4-triazin-3-ylthiol (CXL) 5-(3-octanamidophenyl)-6-benzotriazolylthiol (CXLI) 4-butyl-l(H)-azepin-2-ylthiol (CXLII) l-(3-phenylpropyl)-2-piperidinylthiol'(CXLIII) l,3-dihexyl-Z-imidazolidinylthiol (CXLIV)2-octylthio-5-thienylthiol (CXLV) S-hexanamido-2-benzothienylthiol(CXLVI) 4-(3-hexanamidophenyl 1,3-dithiol-2-ylthiol (CXLV-I) 4-3-octanamidophenyl 1,3-oxathiol-2- ylthiol (CXLVII)4-hexyl-3-thiamorpholinylthiol (CXLVIII)4-(4-phenylbutyl)-1,4-thianin-3-ylthiol (CXLIX)4-(3-octanamidophenyl)-2-selenazolylthiol (CL)5-benzamido-2-benzoselenazolylthiol (CLI)5-acetamido-3-benzoisoselenazolylthiol (CLII)4-(3-hexanamidophenyl)-3-isoselenazolylthiol (C-LIII)2-naphthaleneselenol (CLIV) l-(3-pentanamidophenyl)-tetrazol-5-ylselenol(CLV) 1-(3-nonanamidophenyl)-tetrazol 5-ylselenol (CLVI)G-Octanamido-l,3-benzoselenazol-2-ylselenol (CLVH)S-pentanamido-1,3,4-selenadiazol-2-ylselenol (CLVIII)S-octanamido-l,3,4-thiadiazol-2-ylselenol (CLIX)2-decylthio-1,3,4-thiadiazol-Z-ylselenol (CLX)2-decylthio-1,3,4-selenadiazol-2-ylselenol (CLXI)oxalic-bis-N-[3-(5-mercaptotetrazol-l-yl)- anilide] (OLXII) disulfide,bis-1-(3-nonanamidophenyl)-tetrazol-l-yl n v (CLXlII-I) disulfide,bis-S-nonanamido-1,3,4-thiadiazol- (CLXIV)1-(3-octanamidophenyl)-5-mercaptotetrazole,

sodium salt (CLXV) 1-(3-nonanamidophenyl)-5-mercaptotetrazole,

potassium salt (CLXVI) 2-octylthio-5-mercapto-l,3,4-thiadiazol, am-

monium salt Thev combination of onium salt and silver bleach inhibitorare brought into contact with the sound track portion of the film in theform of a solution. The solvent can be any solvent which will dissolvealone or with other solvents, the onium salts and the silver bleachinhibitors, and is compatible with hydrophilic colloid silver halideemulsions, the supports for these emulsions, and the aqueous processingof such emulsions. The solvent can be for example, lower alkyl alcoholsuch as methyl alcohol, ethyl alcohol, isopropyl alcohol and the like,but

is preferably'predominantly aqueous.

The concentration of onium salts in the solution can vary widely andtypically range from about 1% weight to 15% weight and preferably fromabout 5% weight to about 10% Weight.

The concentration of silver bleach inhibitor in the solutions can alsovary widely and typically range from about 0.1% weight to about 3%weight and preferably range from about 0.5% weight to about 2% weight.

In addition to the onium salt and the silver bleach inhibitor, thesolution can also contain a silver halide solvent such as an alkalimetal or ammonium thiosulfate, thiocyanate or sulfite or mixtures ofthese compounds. As a result, the residual silver halide in the soundtrack area is fixed out at the same time the silver image is protectedagainst subsequent bleaching. However, silver halide solvent can beomitted from the solution.

The process of the invention is generally applicable to the productionof silver auxiliary or sound track images in color film. Typically, thecolor film is comprised of one .or more (generally three) color-formingunits, each unit comprising one or more (generally one or two) silverhalide emulsion layers. The color-forming units can be of the type whichdo not contain incorporated photographic couplers. In this event, thephotographic element is processed in the presence of a coupler-developercomposition. This composition contains both a diffusible aromaticprimary amine color developing agent and a diffusible photographiccoupler. The oxidized color developing agent resulting from thedevelopment of a latent silver halide image reacts with the ditfusiblephotographic coupler to produce a nondiffusible dye at the site ofdevelopment. The process, however, is particularly useful for colorfilms of the type having color-forming units containing incorporatedcouplers. This type of film is developed in the presence of an aromaticprimary amine color developing agent. The oxidized color developingagent resulting from the development of the latent silver halide imagein this type of film reacts with the incorporated coupler at the site ofdevelopment to produce a nondilfusible dye. The photographic couplerswhether contained in a coupler development composition or incorporatedinto the color-forming units are well known to those skilled in thephotographic art. For example, S-pyrazolone couplers are typically usedto produce magenta dye images, phenolic, including naphtholic, couplersare typically used to produce cyan dye images and open-chainketomethylene couplers are typically used to produce yellow dye images.The above films can either be negative-positive print films or reversalprint films.

The auxiliary silver image record or sound track record can be comprisedof either silver or silver plus a dye. The record is comprised of silverif the film is the reversal film and is comprised of silver and a dye ifthe film is a negative-positive print film. Since the treatment of theauxiliary silver image record or silver sound track record is subsequentto initial development and prior to color development and/or bleaching,the auxiliary or sound track image to which the film is exposed is anegative image which will result in a positive image upon initialdevelopment.

The sound track image can be either a variable density sound track or avariable area sound track. The auxiliary silver image record can be ofany image which one wishes to retain in some part of the film. Forexample, the auxiliary silver image can be a synchronizer signal printedin the sound track area to accomplish such purposes as the changing ofslides in a multimedia program or to accomplish any other such purposeas one can wish to associate with motion picture films.

The treatment of the sound track to prevent subsequent bleaching of thesilver therein is accomplished subsequent to initial development and inthe case of reversal films prior to color development. In the case ofnegative-positive print films the sound track treatment is prior tobleaching.

In the case of reversal films, reversal development of the residualsilver halide in the sound track must not occur. This is because thateven though the silver developed during reversal development will nothave been treated to prevent its subsequent bleaching, dyes will formwherever reversal development takes place. These dyes, particularly thecyan dye, will interfere with the quality of sound track obtained. Toprevent reversal development of the residual silver halide in the soundtrack the picture area can be fogged with light rather than by using achemical fogging agent. Alternatively, the onium salt-silver bleachinhibitor solution can contain sufficient silver halide solvent to fixout the residual silver halide in the sound track area. In this case,the film can be treated with a chemical fogging agent prior to orconcurrent with reversal development.

The application of the onium salt-silver bleach inhibitor solution toonly the sound track area of the film can be accomplished in anyconvenient manner such as passing the edge of the film bearing the soundimage through a bath containing the onium salt and the bleach inhibitoror by passing the area of the film under a roller which is wet with thesolution containing these compounds.

The length of time the sound track. portion of the film is contactedwith this processing solution can be varied considerably and depends tosome extent on the concentration of the compounds in the solution.Especially good results are obtained with contact times of to seconds inbaths containing about 50 to 150 grams per liter ammonium salt and about5 to 20 grams per liter of silver bleach inhibitor. However, contacttimes can range up to 5 to 10 minutes or more if needed. The contacttimes and relative concentrations of the compounds in the solution canbe adjusted as desired.

The improved process of this invention is useful in preventing thebleaching of the silver sound image by strong bleaching solutions suchas acid or alkaline ferricyanide solutions and dichromate solutionswhich are used to convert silver in color photographic films to saltssoluble in fixing solutions. This process is particularly useful inpreventing bleaching by very strong bleaching solutions such as thosewhich contain to 25% weight of the bleaching compound such as theferricyanide or dichromate compound. These strong bleaching solutionsare designed for use in high speed processing to rapidly convert thesilver to a soluble silver salt.

The process of this invention provides a highly convenient method forretaining silver image in the sound track area of a color film. Itrequires but one separate treatment of the sound track portion of thefilm and allows obtaining the metallic silver sound track in a colorreversal film from a negative sound original.

A further understanding of my improved method of processing photographicelements can be had by referring to the drawing in the Bevis et a1.application referred to hereinabove, and which drawing is incorporatedherein by reference. This drawing depicts diagrammatically andsequentially the processing of a photographic element shown incross-sectional view to produce a color picture record and a silversound record. The processing is according to the novel method of thatinvention and differs from my improved method of processing only in thecomposition of the bleach inhibitor composition.

The following example is included for a further understanding of theinvention, it being understood that other bleach inhibitors and oniumsalts as described above can similarly be utilized.

A multilayer color photographic motion picture reversal print film witha picture record area and a sound track record area and bearing on atransparent cellulose acetate film support, in order from the support, aphotographic color-forming unit primarily sensitive to the red region ofthe visible spectrum comprising a gelatino silver halide emulsion layercontaining a nondiffusible cyanforming phenolic coupler, a photographiccolor-forming unit primarily sensitive to the green region of the.visible spectrum Comprising a gelatino silver halide emulsion layercontaining a nondiffusible magenta dye forming 5- pyrazolone coupler, ayellow filter layer, and a photographic color-forming unit primarilysensitive to the blue region of the visible spectrum comprising agelatino silver halide emulsion layer containing a nondifiusible yellowdye forming open-chain ketomethylene coupler is exposed to a multicolorpicture record multi-step test object and a sound record negativemulti-step test object and processed as follows:

Tempera- Bath Time ture, C.

1. Prehardener 2 minutes, 30 seconds- 35 2. Neutralizer 30 seconds. 353. First developer 2 minutes, 15 seconds. 38 4. First ston 30 seconds 355. Wash do 38 6. Sound track bath 10 seconds 38 7. Wash- 30 seconds 388. Color develop 2 minutes, 30 seconds- 43 9. Second p 30 seconds 35 10.Washdo 38 11. Bleach 1 minute, 30 seconds 35 12. Fix. do 35 13. Washlminute 38 14. Stabilize. 30 semnds 35 The chemical composition of theabove processing baths is as follows:

( 1 Prehardener:

Water m 800.0 p-toluenesulfinic acid (sodium salt) g 1.0 Succinaldehyde,bis, bisulfite g 8.5 Magnesium sulfate, heptahydrate g 257.0 Sodiumsulfate ....g-- 75.0 Sodium bromide g 2.0 Sodium acetate g 15.0 Formalin(37% by volume aqueous formaldehyde solution) ml 27.0 Glacial aceticacid ml 2.4 N methyl benzothiazolium-p-toluene sulfo nate g .03 Water to1.0 liter.

(2) Neutralizer:

Water ml 800.0 Hydroxylamine sulfate g 18.0 Sodium bromide g 17.0Glacial acetic acid ml.. 10.0 Sodium hydroxide g 6.8 Sodium sulfate g50.0 Water to 1.0 liter.

(3) First developer:

Water ml 800.0 Sodium tetraphosphate g 2.0 Sodium bisulfite 8.01-phenyl-3-pyrazolidone g .35 Sodium sulfite g 37.0 Hydroquinone g 5.5Sodium carbonate (anhydrous) g 28.2 Sodium thiocyanate g 1.38 Potassiumiodide (0.1% by weight aqueous solution) ml 13.0 Sodium bromide g 1.30Water to 1.0 liter.

(4 and 9) First and second stop bath:

Water ml 800.0 Glacial acetic acid ml 30.0 Sodium hydroxide g 1.65 Waterto 1.0 liter.

(6) Sound track bath:

Hexadecyl trimethyl ammonium bromide g 100.01-phenyl-5-mercaptotetrazole g 10.0 Ammonium thiosulfate (60% solution).mL. 1700 Water to 1.0 liter.

(8) Color developer:

Water ml 800.0 Nitrilo (trimethylene phosphonic acid) sodium salt ml 3.0Benzyl alcohol g 4.5 Sodium sulfite g 7.5 Trisodium phosphate- 12H O g36.0 Sodium bromide g 0.9 Potassium iodide (0.1% w. solution) Sodiumhydroxide Citrazinic acid g 1.5 4-amino-3-methyl-N-ethyl-N ([3methanesulfonamidoethyl)-aniline sesquisulfate monohydrate g 1 1.0Ethylenediamine g 3.0 Water to 1.0 liter.

(11) Ferricyanlde bleach:

Water ml. 800.0 4 Sodium bromide g 43.0 Sodium ferrocyanide(decahydrate) g 245.0 Potassium persulfate g 67.0 V Borax (Na B O -H O)g 1.0 Carbowax 1540 g 3.6

. Water to 1.0 liter.

(12) Fixing bath:

- Water ml 800.0 EDTA (disodium salt) g 0.5 Sodium thiosulfate(pentahydrate) g 204.0 Sodium sulfite g 10.0 Disodium phosphate g 15.0

Water to 1.0 liter.

(14) Stabilizing bath:

Renex 30, Atlas Chemical (a polyethylene ether alcohol) ml 0.14'Formalin (37% w. solution) ml 6.0 Water to 1.0 liter.

The step 6 sound track bath is applied to only the sound track area ofthe film. Because the sound track bath contained a silver halidesolvent, reversal fogging was accomplished with a'chemical fogging agentin the color developenSilver densities are measured at 900 nm. 1on adensitometer at D The silver density of the sound track ofa filmprocessed as above is 1.57. The silver density of the sound track of afilm processed as above except omitting the 1-phenyl 5 mercaptotetrazolefrom the sound track bath is 1.18. The silver density of the sound trackof a film processed as above except omitting the hexadecyl trimethylammonium bromide from the sound track bath is 0.08. When the above filmis processed as above except that the sound track bath contains otheronium salts and other silver bleach inhibitors, similar results areobtained. When the above film is exposed to a multicolor image and anegative sound record and processed as above, films are obtained havingyellow, magneta and cyan picture records substantially free of silverand excellent silver sound records.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can 'be effected within the spirit andscope of the invention.

I claim:

1. In the process of producing a picture record and an auxiliary silverimage record in an imagewise exposed photographic element having atleast one silver halide emulsion layer which comprises developing saidexposed element to form a picture record comprising silver and anondiffiusible dye and an auxiliary image record comprising silver andbleaching and fixing the element to remove the silver of the picturerecord,the improvement which comprises contacting the silver of theauxiliary image but not the'silver of the-picture re'cordprior tobleaching with a mixture of a silver bleach inhibitor and a ditIusi-bleonium salt to retain at least a portion of the silver of the auxiliaryimage record during said bleaching.

2. The improvement of claim 1 wherein said onium salt is a quaternaryammonium salt.

3. The improvement of claim 2 wherein said silver bleach inhibitor hasan acidic thiol or selenol group and wherein said quaternary ammoniumsalt is a tetraalkyl quaternary ammonium salt.

4. The improvement of claim 3 wherein said silver bleach inhibitor is amercapto alkanoic acid, a thioaryl or a mercapto-substitutedheterocyclic compound containing 5 to 6 atoms in the ring, said ringcontaining at least one nitrogen atom.

5. The improvement of claim 4 wherein said silver bleach inhibitor is amercaptobenzoxazole, a mercaptobenzothiazole, a meracaptobenzimidazole,a mercaptothiadiazole, a mercaptotriazole or al-phenyl-S-mercaptotetrazole.

6. In the process of producing a color picture record and a silver soundtrack record in an imagewise exposed photographic element having atleast one silver halide emulsion which comprises developing said exposedelement to form a picture record comprising silver and a nondiffusibledye and a sound track record comprising silver and bleaching and fixingthe element to remove the silver of the picture record, the improvementwhich comprises contacting the silver of the sound track record but notthe silver of the picture record prior to bleaching with a mixture of asilver bleach inhibitor and an onium compound which retains at least aportion of the silver of the sound track record during said bleaching.

7. The improvement of claim 6 wherein said silver bleach inhibitor has aformula selected from the group consisting of:

Ra eA e-x ye wherein:

a represents 0, 1, 2, 3, 4, 5 or 6;

X represents a member selected from the group consisting of sulfur andselenium;

R R R and R each represents a member selected from the group consistingof nitro, halo, an alkyl group, an aryl group, a thio group containingfrom 3 to 22 carbon atoms, an amido group containing from 4 to 22 carbonatoms, a carbonyl group, 'a carbamoyl group, an alkoxy group and anaryloxy p;

R represents a member selected from the group consisting of hydrogen andan acyl group;

, Y represents a basic cation;

A A A and A each represents a member selected from the group consistingof a carbonyl group, a thiocarbonyl group, a carboxymethylene group, a 3to 6 membered carbocyclic ring and a 3 to 6 membered heterocyclic ringcontaining at least one carbon atom and at least one heteroatom selectedfrom the group consisting of nitrogen, oxygen, sulfur and selenium suchthat R R R and R do not represent a carbonyl group, a carbamoyl group oran amido group when A A A and A represent a carbonyl group or athiocarbonyl group and such that the grouping R -'A the grouping R -Athe grouping R {-A and the grouping -R,, GA each represents a moietyhaving a molecular weight of from to 1,000 and wherein said onium salthas a formula selected from the group consisting of:

1: GB n R 8-3.

wherein R to R each represents alkyl or aryl, X" represents an anion andZ and Z each represents the nonmetallic atoms necessary to complete aheterocyclic ring containing 5 to 6 atoms in the heterocyclic ring, saidatoms being selected from the group consisting of carbon, nitrogen,oxygen, selenium and sulfur.

8. The improvement of claim 7 wherein the grouping 'R tA R A R "'A"-)and the grouping 'R,, {-A represent a member selected from the groupconsisting of a benzoxazole nucleus, a benzothiazole nucleus, abenzimidazole nucleus, a thiadiazole nucleus, a triazole nucleus and al-phenyltetrazole nucleus and said onium salt is a tetraalkyl quaternaryammonium salt.

9. In a process of producing a color picture record and a silver soundtrack record in an imagewise exposed photographic element having aplurality of superposed picture recording photographic image-formingunits comprising at least one silver halide emulsion layer which processcomprises developing said exposed element to form a picture recordcomprising silver and a nondiffusible dye and a sound track recordcomprising silver and bleaching and fixing the element to remove thesilver of the picture record, the improvement which comprises contactingthe silver of the sound track record but not the silver of the picturerecord prior to bleaching with a mixture of a silver bleach inhibitorand an onium compound to retain at least a portion of the silver of thesound record during said bleaching.

10. The improvement of claim 9 wherein said silver bleach inhibitor isselected from the group consisting of a mercaptoalkanoic acid, athioaryl and a mercapto-substituted heterocyclic compound containingfrom 5 to 6 atoms in the ring, said ring containing at least onenitrogen atom and wherein said onium compound is a tetraalkyl quaternaryammonium salt.

11. The improvement of claim wherein said picture recording photographicimage-forming units contain in each of said units at least onenondiir'using photographic color coupler which reacts with oxidizedaromatic primary amine color developing agent to form a nondiflusibledye essentially complementary in color to the sensitivity of theemulsion in which it is incorporated.

12. In the process of producing a color picture record and a silversound track record in an exposed photographic element having a pluralityof picture recording photographic units comprising at least one silverhalide emulsion layer which process comprises developing said exposedelement to form a picture record comprising silver and a nondifiusibledye and a sound track record comprising silver, the improvement whichcomprises contacting the silver of the sound track record but not thesilver of the picture record prior to bleaching with an aqueous solutionof hexadecyltrimethyl ammonium bromide and 1-phenyl-5-mercaptotetrazole.

13. A photographic processing composition comprising a silver bleachinhibitor and an onium salt.

14. A photographic processing composition comprising an aqueous solutioncontaining a silver bleach inhibitor and an onium salt.

15. A photographic processing composition comprising a silver bleachinhibitor having a formula selected from the group consisting of:

a represents 0, 1, 2, 3, 4, 5 or 6;

X represents a member selected from the group consisting of sulfur andselenium;

R R R and R each represents a member selected from the group consistingof nitro, halo, an alkyl group, an aryl group, a thio group containingfrom 3 to 22 carbon atoms, an amide group containing from 4 to 22 carbonatoms, a carbonyl group, a carbamoyl group, and alkoxy group and anaryloxy p;

R represents a member selected from the group consisting of hydrogen andan acyl group;

Y represents a basic cation;

A A A and A each represents a member selected from the group consistingof a carbonyl group, a thiocarbonyl group, a carboxymethylene group, a 3to 6 membered carbocyclic ring and a 3 to 6 membered heterocyclic ringcontaining at least one carbon atom and at least one heteroatom selectedfrom the group consisting of nitrogen, oxygen, sulfur and selenium suchthat R R R and R do not represent a carbonyl group, a carbamoyl group oran amido group when A A A and A represent a carbonyl group or athiocarbonyl group and such that the grouping R -GA the grouping RJKA),the grouping R t-A and'the grouping R rf-A i each represents a moietyhaving a molesular weight of from to 1,000 and an onium salt having aformula selected from thegroup consisting of:

e I x III. .2 I I o \N/ X 12 11 IV. n

ru-r iR xand v u ls, Ru X wherein R to R each represents alkyl or aryl,X represents an anion and Z and Z v each represents the nonmetallicatoms necessary to compete a hetero! cyclic ring containing from 5 to 6atoms in the heterocyclic ring, said atoms being selected from the.group consisting of carbon, nitrogen, oxygen, seleniumand sulfur. v v

16. A photographic processing composition of claim 15 wherein thegrouping R {-A the grouping R (-A the grouping R tA -y and the groupingR {A each represents a heterocyclic nucleus containing 5 to 6 atoms inthe heterocyclic ring, said ring containing at least one nitrogen atom,X represents sulfur and said onium salt is a tetraalkyl quaternaryammonium salt.

17. A photographic processing composition comprising a silver bleachinhibitor, and onium salt and a silver halide solvent.

18. A photographic processing composition having a pH of about 6 to 8comprising an aqueous solution containing 0.1% weight to 3% weightl-phenyl-S-mercaptol8 tetrazole and 5% weight to 15% weight hexadecyltrimethylammonium bromide.

References Cited UNITED STATES PATENTS 3,083,097 3/1963 Lassig et al96-29 L 3,210,189 10/1965 Von Wartburg 9659 J. TRAVIS BROWN, PrimaryExaminer 10 A. T. SURO PICO, Assistant Examiner US. Cl. X.R. 96--60 R,39

' wnnumu ukmemu Humane v- QEKEZMCAEE @51 @DRREQTEQN Patent No. 3 s 705Dated December l2 1973 William 5. Lane Inventofls') It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 17, line 9, the firstf'and" should be '--an---.

Signed and sealed this 10th day of July. 1973 (SEAL) Attest:

EDWARD M.FLETCHER',JR. Rene Te tmeyer Attesting Officer Actingommissioner of Patents

